The present invention relates to a novel method for the preparation of N-phosphonomethylglycine of formula (I), a herbicidal component which is known in the agricultural chemical art as glyphosate. ##STR2##
German Offen. No. 2,700,017 discloses a process for producing N-phosphonomethylglycine by a process in which 1,3,5-tricarboethoxymethylhexahydro-s-triazine is reacted with dialkylphosphite under reflux followed by hydrolysis. This process requires high reaction temperature for a few hours to react triazine with dialkylphosphite to make N-phosphonomethylglycine triesters. Furthermore, removal of high boiling solvent such as benzene, toluene etc. before hydrolysis also makes this process laborious. We now have discovered that a simple and mild process for the preparation of N-phosphonomethylglycine triesters. The present invention involves the preparation of N-phosphonomethylglycine triesters of the formula II by reacting ),3,5-tricarboalkoxymethylhexahydro-s-triazine of the formula III with trialkylphosphite of the formula IV in the presence of titanium tetrachloride and followed by hydrolysis to make N-phosphonomethylglycine of the formula I. The following reactions illustrate the present invention; ##STR3##
Wherein, R and R.sup.1 are selected from the group consisting of alkyl having 1 to 2 carbon atoms which is inert to the coupling reaction Titanium tetrachloride is added into 1,3,5-tricarboalkoxymethylhexahydro-s-triazine in proper solvent to give dark yellow colored solution at -10-0.degree. C. Into this solution was added trialkylphosphite and the resulting reaction mixture was stirred at the same temperature. Without titanium tetrachloride the reaction has not proceeded at all. The amount of titanium tetrachloride is 3-3.5 mole equivalents to 1,3,5-tricarboalkoxymethylhexahydro s-triazine. The solvent for the reaction is any one of methylene chloride, chloroform, carbon tetrachloride, trichloroethylene without affecting the reaction yield The way to carry out the reaction is that 3.5 mole equivalent of titanium tetrachloride is added to one more equivalent of 1,3,5-tricarboalkoxymethylhexahydro-s-triazine followed by addition of 3 mole equivalent of trialkylphosphite at -10-0.degree. C. In case of large scale reaction, portionwise addition of reactants is recommended to control the reaction temperature. At first 1.5 mole equivalent of titanium tetrachloride was added into 1 mole equivalent of 1,3,5-tricarboalkoxymethylhexahydro-s-triazine in proper solvent followed by addition of 1 mole equivalent of trialkylphosphite. Then 1 mole equivalent of titanium tetrachloride was added followed by addition of another 1 mole equivalent of trialkylphosphite. Finally residual one mole equivalent of titanium tetrachloride and one mole equivalent of trialkylphosphite were added.
The present invention relates to a process for hydrolysis of N-phosphonomethylglycine triesters with aqueous inorganic acids such as hydrochloric acid, sulfuric acid, or hydrobromic acid. Using volatile acid such as hydrochloric acid or hydrobromic acid has an advantage to be concentrated under reduced pressure easily after hydrolysis. Therefore, hydrolysis of N-phosphonomethylglycine triesters with hydrochloric acid or hydrobromic acid under reflux to give white solid N-phosphonomethylglycine. Hydrolysis of N-phosphonomethylglycine triesters is also carried out at 80-100.degree. C. for 2 hours with aqueous hydroxide solution such as NaOH or KOH. The final product N-phosphonomethylglycine was obtained after acidification of its salt obtained from the hydrolysis with aqueous hydroxide solution.
1,3,5-tricarboalkoxymethylhexahydro-s-triazine used in this invention was obtained from the reaction of glycine alkoxyester with formaldehyde.
All of the products in this invention were fully identified by elemental analysis and spectrometry.